All purpose



ALL PUnPosnnnrERon-NnnAa CharlesfF. Jelinek, Parkwootl, Easton, Pa, Raymond L.

Mayhew, Phillipsliurg, N. L, and John A. Yeager, Easton, Pat, assignors to'General Aniline a; Film Cor poration, New York, N. Y., a corporation-of Delaware No Drawing. Application May 12,1953, Serial No. 354,646

11' Ciaims. (Cl; 252-121) This invention relates to the production-ofa deter-gent bar or. cake and more particularly to an-all purpose detergent bar suitable foruse insoft. water, hard Water and seawater.

It is known. that either hard' water or sea water seriously impairs 'the-eflicie'ncy of soap in regard to detergency and lat-hering due to' the-precipitation: of. the calcium and magnesium. salts of soaps. The additicniof synthetic detergents to soap to improve performance in hard and sea water is an art that has: been: practiced for many years but themajor objection .tosuclr combinations is poor lather. On the other hand, uon-soap-cont ain'ing synthetic detergent bars are not satisfactory due to high cost, hygroscopicity, unsatisfactory solubility characteristics, defatting actionron the skin, lack of lubricating effect-and slipperyrfeel usually associatedwith soap, poor working; properties; standard. soap machinery, brittle ness and poor. cohesion of the barzitself'. A large number'ofibinders andfillers have been used' in conjunction with synthetic; detergentsin. an attempt to obtain a detergentzbar-zresemhling in. activity theusual toilet soap bar Whenused in: soft Water; However, although a con-siderable amount of WOIk.l'1218- beenidone to provide an all purpose detergent bar, none has been truly satisfactory. The followingimay. beconsidered to b'e:the major propcrties: desirable insa; good all purpose detergent bar;

-1.. Good. deter-gency onrthehuman; skim-and fabrics and hard surfaces. in allkindsof water including-hard, soft, sea coldiand hot;

"2; Good soap-like lathering qualities intall types. of water, particularly when used on the skin.

3. Mild'and'non-injurious to-the skin.

4; little or-no tendency towards softening, blooming, crystall-izing, cracking, drying or decomposingunder ordiw nary use and storage conditions.

'55 Pleasing-appearance, feel and' odor.

6. Ability to be produced in standard soa'p mixing equipment.

Attemptg to provide an all purposedetergent' haruvith the aforementioned proper-ties are complicatedand rendered difiiculti by the following facts.

.1-.. Detergents whichr foamr'poorly at the lower concentrations commonlytusedt in'standardifoamz test-s frequently lather; copiously when used atihigher; concentrations such as i uobtained in washing thehands 2.. AlLingredients in the. bar should-have approximately the same rate of. solubility or dispersibility in order to prevent pitting, grittiness, and the-like. 31 The rate of solubility. should be approximately the same in cold water as itis. in hot water, andshould not beun'dul'y high. in order to prevent rapid dissolution when left in water;

4. Some detergents leave sticky or other objectionable residues on the skin.

5: Calcium and magnesiumsalts of'fatty acids formed in situ will seriously impair the lather of many surfactants in certain concentration ranges.

Q6 Patented Feb;

6. Many surfactantstwhich have satisfactory detergent and lathering properties when. used in soft water; have unsatisfactory properties in hard water and 'sea water. This also applies. to soap.

7. Many surfactants which have good detergent and foaming properties by themselves are? unsatisfactory when mixed with soap and certain other surfactants.

it is an object of this invention to provide an all 'p'urposerdeterg'entzbarwhichiwill possess substantially all of the above mention'edvmajor: propertiesdes'lrable in a-good all purpose detergent bar. It is another object of this invention to provide'a detergenfbar capable of p'roducing a satisfactory lather in hot 'an'd cold, soft, hard and sea Water. It is stillanother object of this invention to provide anall purposedetergent bar which will-be nontoxic and non irritating 't'otliehum'anskin; A still fu'rfne'r object of this invention is to provide a detergent har capable of satisfactory performance inwater of any degree of hardhess-from-ze-ro to'the hardness of sea water and: at any teinperatureof from 0 C. to C. for washing dishware and kitchen utensils and. the like, for hand laundering ofclothing, for useas a'general purpose toilet soap, and for. shavingpur-poses. Still another object of this invention is to provide a'd'etergent barhaving the properties-ofa good grade of soft water toilet soap. Other objects and advantages-will appear as the description proceeds.-

The above objects are a-ttained by the instant invention which is directed to-the production of a detergent bar comprising (A) a-syntheticorganic anionicdetergent selected from the groupbonsisting of the water-soluble alkali metal and ainine salts of higheraliphatic sulfates and sulf-onates eontaining a hydrocarbon radicalwith at least ll carbon ato'ms in a straight chain, and alkyl aryl sulfates and sulfonates containing at least one-alkylside chain radical of at least 8 carbo'natoms, B) a synthetic organic anionic lathering agent selected from the group consisting of'tiie water soluble alkali metal and" amine salts of lower alkyl aryl sulfates and sulfonat'es containing" at least one alkyl side chain radical of from 2' to 6 carbon atoms, and (C) a syntheticorganic anioniclathen ingagent selectedfrom' the groupconsi sting'of the water soluble alkali metal and amine salts' of lower aliphatic sulfates and sulfonate'scontaining an open (straight or branched) chain hydrocarbonradical'of from 3' to9car bon atoms; The aforementioned detergent liar jmay 'optionally and preferably co'ntaina water-soluble soap se' lected from 'thagroup consisting of"the water-soluble alkali metal and amineisalts ofihigher aliphatic mono"- carbox-yli-c acids. The detergent bar may also. contain suitable binders, fillers, perfumes-, salts, colors, fungicides, germicides; antiseptios and thelike;

As the-longcliain' detergents suitable for use as component'A-in theinstantirivention, there maybe mentioned long chain alkyl aryl sulfonates' such as sodium o'c'tyl nonyl dodecyl, decyl -and tetra'decylbenzene sulfonat'es, Nlong chain acylv N alkyl taurates such as'sodium oleoyl methyltaurate,='sodium pal'niitoyl methyl taurate, sodium or potassium lauroyl methyl taurate, and the correspond ing' acyl ethyltauratesslong chainalkyloxyethylene sulfates such asisodium: or. potassium laurylpo'lyoxyethylene sulfate, sodium laurylmonoonyethylene: sulfate, sodium octadecylpolyoxyethylenesulfate, and sodiumcetylpolyoxyethylene sulfate, long chain alkyl' aryl oxy'ethylene sulfates suchraslammonium, sodium, or potassium nony-L, octyl-, and tridecylphenol monoand polyoxyethylene. sulfates, long chain alkyl sulfates such. as sodium laur'y l and steanylsulfates, long ehain alkylisethionatessuch.-as sodiumoleic isethionate, sodiiun lauric isethionate and the like. Miiitures of the above mentioneddetergents may also be employed. Component A may be used in quan- 3 tities varying fromabout 5 to 90 percent, and preferably from about 5 to 50 percent by weight of the bar.

As the lower alkyl aryl lathering agent suitable for use as component B in the instant invention there may be mentioned sodium diisopropyl naphthalene sulfonate, sodium isopropyl naphthalene sulfonate, sodium diisobntyl naphthalene sulfonate, sodium isobutyl naphthalene sulfonate, sodium isohexylbenzene sulfonate, monobutyl biphenyl sodium monosulfonate, monobutylphenylphenol sodium monosulfonate, dibutylphenylphenol sodium disulfonate, and the like. Component B may be used in quantities varying from about 2.5 to 75 percent but more preferably from about 5 to percent by weight of the bar.

As the lower aliphatic lathering agent suitable for use as component C in the instant invention there may be mentioned the lower alkyl sulfates and sulfonates such as the sodium sulfate derivative of 2-ethyl hexanol-l, sodium 2-ethyl-1-hexenyl sulfonate, sodium isooctyl sulfonate, sodium isononyl (also triisopropylene) sulfonate, lower alkyl esters of aliphatic sulfopolycarboxylic acids such as sodium diamyl sulfosuccinate, sodium diisobutyl sulfosuccinate, sodium dihexyl sulfosuccinate, sodium dioctyl sulfosuccinate, sodium triamyl sulfotricarballylate, sodium triisobutyl sulfotricarballylate, and sodium tri-n-butyl sulfotricarballylate, and the like. Component C may be used in quantities varying from about 2.5 to 75 percent, but more preferably from about 5 to 25 percent by weight of the bar.

As the soap which is preferably employed in the detergent bar of the instant invention, there may be mentioned the water soluble salts of myristic, palmitic, stearic, behenic, oleic, lauric, abietic, capric, caproic, ricinoleic, linoleic, hydrogenated and dehydrogenated abietic acids, and the surface active hydrolysis products of tallow, cocoanut oil, cottonseed oil, soy-bean oil, peanut oil, sesame, linseed oil, olive oil, corn oil, castor oil and the like. While soap is not essential in the formulation, it is preferable to have from about 25 to 75 percent by weight of the bar present for the purpose of improving the feel, appearance, working properties and the like.

While the water-soluble sodium salts of the aforementioned detergents, lathering agents, and soaps are generally preferred, other alkali metal and amine salts may be employed, as for example those with potassium, ammonium, lower alkyl amines such as methylamine, ethylamine, propylamine, and isopropyl amine, lower alkylolamines such as mono-, diand triethanoland isopropanolamines, cyclic amines such as cyclohexylamine, morpholine, and-pyrrolidine, and the like.

Suitable additive, e. g. binders, fillers, builders and the like may be added to the detergent bar of the instant invention to provide properties regarded as desirable in any particular instance. These may include carboxymethyl cellulose, polyethylene glycol, starch (substituted, degraded or undegraded) lignin, alginates, copolymers of maleic anhydride with styrene and polyvinyl alkyl ethers and the like, urea, zein, lecithin, lanolin, talc, salts such as borax, calcium chloride, magnesium chloride, sodium sulfate, sodium phosphate, tetrasodium pyrophosphate, and sodium tripolyphosphate, oxides and hydroxides such as magnesium oxide, sodium hydroxide, potassium hydroxide and titanium hydroxide, dyes, pigments, perfumes and the like.

These supplementary agents may be used to control the rate of solubility of the bar, improve slip and feel, stabilize it against changes in humidity which cause softening or drying out, improve its appearance and odor, serve as builders and thelike. Their use however must be carefully regulated to prevent undesirable and disadvantageous properties from resulting. Thus, some inorganic salts are too soluble and are leached out of the bar, mak ing it rough. Others are insoluble or only slightly soluble so that they are left as rough gritty particles on the surface of the bar when the more soluble portions are dissolved out. Many crystallize out on the surface of the bar during storage. Some are too hygroscopic, causing excessive softening of the bar on storage in humid conditions. Most of them make a very hard and dense bar. Those with a negative heat of solution make the bar feel cold on the skin during use. Varying amounts of inorganic salts such as sodium sulfate, sodium chloride, ammonium chloride and the like are present in certain of the surfactants employed in the bar as manufactured, but generally and preferably such amounts total no more than about 25 percent by weight of the bar. Bars containing clay, bentonite or rosin usually have a gritty feel and insufficient slip. Some are very dark in color making a very unattractive bar.

Small amounts of waxes, oils, fats and greases improve milling of the ingredients by plasticizing the mixture. They also serve as lubricants in aiding release of the bar from the dye in the stamping operation. Residues left on the skin after washing act as emollients to overcome the defatting efiect of the detergents. However, they have a serious defoaming effect on the surfactants in the composition particularly when employed in too large an amount. Carboxymethylcellulose may be added to improve whiteness retention for fabric -detergency and as a foam stabilizer and skin beneficient. Similarly, lanolin when used in emollient amounts to overcome the defatting effect of the detergents, has a detrimental effect on lathering properties.

Starches, gums and dextrines are unsatisfactory in large amounts in that they tend to reduce the slip of the bar and dry out, causing cracking and crumbling of the bar. Those of low solubility are preferred since they reduce the rate of consumption of the bar.

In the preferred embodiment of this invention, the detergent bar contains a mononuclear long chain alkyl aryl sulfonate, more specifically sodium dodecyl benzene sulfonate, as component A, a lower alkyl naphthalene sulfonate, more specifically sodium diisopropyl naphthalene sulfonate as component B, a salt of a lower alkyl ester of an aliphatic sulfopolycarboxylic acid, more specifically sodium diamyl sulfosuccinate, as component C, and a water-soluble soap such as sodium tallow soap, in addition to small amounts of carboxymethylcellulose and perfume. A bar manufactured in accordance with this preferred embodiment has highly satisfactory properties for handwashing, shaving, dishwashing, and cotton detergency in soft, hard or sea water. After more than twenty months of storage through humid summer and dry winter conditions, it still had a smooth soap-like appearance, with no evidence of blooming or cracking, and at no time during this period did it exhibit undue softness or brittleness. When used for washing and shaving, it likewise does not exhibit undesirable pitting, blooming, slushing, or cracking.

The bar in accordance with the instant invention may be produced in well known manner by a framing, milling or similar process. In making frame bars, all the ingredients are mixed at elevated temperatures in a crutcher with sufiicient water to permit easy stirring. The mass is then poured into wooden frames to cool, solidify and partially dry after which the frame is removed, and the soap block cut into pieces and stamped in a soap press. In the milling process all of the materials for making the bar are mixed in an amalgamator, preferably passed through a roller mill for one or more times to assure a thorough mixing while adding sufiicient water to provide the proper viscosity, and the milled mass then compressed and extruded from a plodder into long bars which are cut into suitable lengths and stamped into the desired shape and size.

The examples in the following table, in which parts are by weight, are illustrative of the compositions of the detergent bars made in accordance with the instant invention. It will be understood thatthe'invention is not limited thereby:

It will be-understood: that the term detergent bar as employed herein and the appended"claims'includes any Table Detergent Latherlng agents 7 Soup, Ex. A B- parts Additional components Type Parts Type Parts Type Parts Type Parts,

1 Na dodecylbenzene sul- 10 Nadiisopropylnaphtha- 10 Na dlamylsuliosucci- 5 50. .Gum No.1iJ8 15 innate. lene sulfonate. 'nate. I i

' Gum N0. 198.... 13 do 5 50 STPB 10 10 50v 7: 50 7 60 5 '50 5 30 15 do... s- 42 Nadihexylsulfosuccinate- 10 47 20 Na dlisobutyl sulfo- 6 51 A succinate. i v 20 Na isooetyl sulfonate.-.- 20. i 37 20 Na lsononylsulfonate'...' 12 45' 20 Nadlamylsulfosueel- 10 37 nate. 20 -do 10 20 -do... 10 "37 20 do. 10 37 20 do 1O 27 20 Na2-ethyl-l-hexenylsul- 10, 5G

fonate. 20 Na dlamyl sulfosucel 10 -40 10 hate: V 20. .....do 10, i8 20 d0 10 j '45- 2 20. 10 -1qas ,3 10 20 d0 10 28 2 10 10 20 d0 10 28 2 10 7 20 -.-do 10 25 10 10 15 do 7 30 5 12 do 20 -do 20 Na, tri-isobutyl sulfo- 10 45 CarboseD 2 carballylate. do 20 d0 20 Na tri-n-butyl sulfo- 10 45 do 2 iii i 1: o b D 2 3. am y su osuceiar ose 20 20 na 10 47 Pine perfume... 11 0 do 20 -.d0 10 do 5 2g 2 ..do 40 -.--.d0 40 ---do 20 NHlnonyl phenol 10 d0 10 d0 5 (C2H40)4 sulfate. H Nadodeeylbenzenesul- 20 Na dusobutylnaphtha- 20 do 1o 47 fonate. lene sulfonate.

All of the detergent bars described in the above table have satisfactory hand Washing lathering properties in tap water and as good or better lathering properties in sea water. The soap employed was in all instances, except in Example 2, a sodium tallow soap. In said Example 2, potassium tallow soap was used.

The parts of sodium dodecylbenzene sulfonate shown in the table comprise about 85 percent of active ingredient and 15 percent of inert ingredients such as sodium sulfate. The parts of sodium diisopropyl naphthalene sulfonate shown in the table comprise about 55 percent of active ingredient and percent of inert ingredients such as sodium sulfate Gum No. 198 is a degraded corn starch. STPP is sodium tripolyphosphate. CMC and Carbose D are carboxymethyl cellulose. Indulin C is lignin. Nu- Film is a substituted starch. Alcolec S is lecithin. Nadex 360 is a corn starch.

While all of the detergent bars described in the table are satisfactory, those of Examples 3 and 29 containing the preferred components, as described above, possess superior properties. The bars of Examples 12 and 31 also have highly satisfactory properties.

detergent composition in a solid, cohesive state in any size or shape. Similarly the recitation of an alkyl or hydrocarbon radical containing a specified number of car bon atoms is to be considered as also including a mixture of radicals of the same type averaging the specified number of carbon atoms. Various modifications and variations of this invention will be obvious to the person skilled in the art and it is to be understood that such modifications and variations are to be included within the purview of this application and the spirit and scope of the appended claims.

What is claimed is:

l. A detergent bar comprising (A) about 5 to 50% by Weight of a synthetic organic anionic detergent selected from the group consisting of the water soluble alkali metal and amine salts of higher aliphatic sulfates and sulfonates containing a hydrocarbon radical with at least 11 carbon atoms in a straight chain, and alkylbenzene sulfates and sulfonates containing at least one alkyl side chain radical of at least 8 carbon atoms, (B) about 5 to 25% by weight of a synthetic organic anionic lathering agent selected from the group consisting of the water solu- 7 .ble alkali metal'and amine salts of alkyl-arylsulfates and sulfonates containing at least one alkyl side chain radical of from 2 to 6 carbon atoms and devoid of alkyl side chain radicals of more than 6 carbon atoms, (C) about 5 to 25% by weight of a synthetic organic anionic lather- -7. A detergent bar as defined in claim 5, in which'component B is sodium diisopropyl naphthalene sulfonate.

8. A detergent bar as defined in claim 5 in which com- -ponent C is sodium diamyl sulfosuccinate.

ing agent selected from the group consisting of the water soluble alkali metal and amine salts of lower branched chain aliphatic sulfates and lower alkyl esters of lower aliphatic sulfopolycarboxylic acids containing an open chain hydrocarbon radical of from 3 to 9 carbon atoms, and from about 25 to 75% by weight of a water-soluble salt of a higher aliphatic monocarboxylic acid.

2. A detergent bar as defined in claim 1 in which component A is an alkyl benzene sulfonate salt containing an alkyl side chain radical of at least 8 carbon atoms.

3. A detergent bar as defined in claim 1 in which com ponent B is an alkyl naphthalene sulfonate salt containing an alkyl side chain radical of from 2 to 6 carbon atoms.

4. A detergent bar as defined in claim 1 in which component.C is a salt of a lower alkyl ester of sulfosuccinic acid.

5. A detergent bar comprising (A) about 5 to 50% by Weight of a water-soluble alkyl benzene sulfonate salt containing an alkyl side chain radical of at least 8 carbon atoms, (B) about 5 to 25% by weight of a water-soluble alkyl naphthalene sulfonate salt containing an alkyl side chain radical of from 2 to 6 carbon atoms and devoid of alkyl side chain radicals of more than 6 carbon atoms, ((1) about 5 to by weight of a water-soluble salt of a lower alkyl ester of sulfosuccinic acid, and from about 25 to 75% by weight of a water-soluble salt'of a higher aliphatic monocarboxylic acid.

6. A detergent bar as defined in claim 5, in which component A is sodium dodecylbenzene sulfonate.

9. A detergent bar comprising about 5 to by weight of sodium dodecylbenzene sulfonate, about 5 to 25% by Weight of sodium diisopropyl naphthalene sulfonate, about 5 to 25 by weight of sodium diamyl sulfosuccinate, and from about 25 to by weight of a water-soluble salt of a higher aliphatic monocarboxylic acid.

10. A detergent bar comprising about 20 parts by weight of sodium dodecylbenzene sulfonate, about 20 parts by weight of sodium diisopropyl naphthalene sulfonate, about 10 parts by weight of sodium diamyl sulfosuccinate, about 47 parts by weight of a water soluble salt of a higher aliphatic monocarboxylic acid, and about 2 parts 'by weight of carboxymethyl cellulose.

l1.'A detergent bar comprising about 20 parts by weight of sodium dodecylbenzene sulfonate, about 20 parts by weight of sodium diisopropyl naphthalene sulfonate, about 12 parts by weight of sodium isonony-l sulfonate, and about 45 parts by weight of a water soluble salt of a higher aliphatic monocarboxylic acid.

References Cited in the file of this patent UNITED STATES PATENTS 1,906,484 Nues slein May 2, 1933 2,176,423 Jaeger Oct. 17, 1939 2,438,169 Hoyt Mar. 23, 1948 2,617,772 Keenan Nov. 11, 1952 2,631,980 Lewis Mar. l7, 1 953 

1. A DETERGENT BAR COMPRISING (A) ABOUT 5 TO 50% BY WEIGHT OF A SYNTHETIC ORGANIC ANIONIC DETERGENT SELECTED FROM THE GROUP CONSISTING OF THE WATER SOLUBLE ALKALI METAL AND AMINE SALTS OF HIGHER ALIPHATIC SULFATES AND SULFONATES SCOTAINING A HYDROCARBON RADICAL WITH AT LEAST 11 CARBON ATOMS IN A STRAIGHT CHAIN, AND ALKYLBENZENE SULFATES AND SULFONATES CONTAINING AT LEAST ONE ALKYL SIDE CHAIN RADICAL OF AT LEAST 8 CARBON ATOM, (B) ABOUT 5 TO 25% BY WEIGHT OF A SYNTHETIC ORGANIC ANIONIC LATHERING AGENT SELECTED FROM THE GROUP CONSISTING OF THE WATER SOLUBLE ALKALI METAL AND AMINE SALTS OF ALKYL ARYL SULFATES AND SULFONATES CONTAINING AT LEAST ONE ALKYL SIDE CHAIN RADICAL OF FROM 2 TO 6 CARBON ATOMS AND DEVOID OF ALKYL SIDE CHAIN RADICALS OF MORE THAN 6 CARBON ATOMS, (C) ABOUT 5 TO 25, BY WEITHT OF A SYNTHETIC ORGANIC ANIONIC LATHERING AGENT SELECTED FROM THE GROUP CONSISTING OF THE WATER SOLUBLE ALKALI METAL AND AMINE SALTS OF LOWER BRANCHED CHAIN ALIPHATIC SULFATES AND LOWER ALKYL ESTERS OF LOWER ALIPHATIC SULFOPOLYSCARBOXYLIC ACIDS CONTAINING AN OPEN CHAIN HYDROCARBON RADICAL OF FROM 3 TO 9 CARBON ATOMS, AND FROM ABOUT 25 TO 75% BY WEIGHT OF A WATER-SOLUBLE SALT OF A HIGHER ALIPHATIC MONOCARBOXYLIC ACID. 